Polymerization process



Patented June 21, 1 938- v POLYMEBIZATION PROCESS Rowland Hill, Biackley, Manchester, England,

Imperial assignor to Chemical Industries Limited, a corporation of Great Britain No Drawing. bpplicationoctober 13, 1938, Se-

rial No. 105,444. In Great Britain October 23,

3 Glaims- (Cl. 280-2) This invention relates to a process for the manufacture of valuable polymerization products from cyclohexene oxide.

It is known to obtain resinous polymers by subjecting cyclohexene oxide to very high pressuresin the presence of an active earth or clay as polymerization catalyst. By an active earth or clay I mean a finely-divided, highly-absorbent clay or earth such as, for example, bentonite, fuilers earth or talc or a diatomaceous earth such as kieselguhr.

In carrying the invention into eflect it is not necessary to use very high pressures. Thus, in presence of active earth catalysts polymerization may conveniently be eflected at atmospheric 2o pressures by the application of moderate heat. Polymerization may be carried out in presence or absence of a solvent or diluent. The reaction after it is initiated is highly exothermic and may be controlled by cooling. After the initial violent as reaction subsides the reaction mixture is heated to maintain reaction temperature until a product. of the desired degree of condensation is obtained.

The polymerization products obtained according to the invention-are usually in the form of a hard, somewhat brittle, transparent mass. The products are readily soluble in organic solvents such as benzene, toluene or turpentine and in dry ing oils such as linseed oil. Becauseof their solubility in organic media and their other physical properties, the polymerization products are valuable ingredients for varnish compositions, nitrocellulose lacquers and the like.

The following example, in which the parts are by weight, illustratesbut does not-limit the invention:

Example One (1) partv kieselguhr is suspended in parts cyclohexene oxide (Organic Syntheses", 5 vol. 5, page 35, London,,1925), the mixture is heated to 100 C. to initiate the reaction in a vessel fitted with areflux condenser. After the viscous mass is then dissolved in benzene, boiled v with a small amount (2 parts) of active carbon and filtered to remove kieselguhr. The benzene is then evaporated from the filtrate by heating at C. under reduced pressure (20-30 mm.). The residue so obtained is a pale straw-colored, 5 hard, somewhat brittle transparent resin. It dissolves readily in cold benzene, toluene or turpentine but is insoluble in cold methylated spirits or ethylene glycol monoethyl ether. It is freely soluble in linseed oil, tung oil or a linseed stand 10 o The resin produced in accordance with the foregoing example is in addition to being compatible with drying oils also compatible with rosin modified glyceryl phthalate resins and other rosin 15 modified polyhydric alcohol-polycarboxylic acidresins. The resin of the foregoing example is also compatible in equal proportions with nitrocellulose and ethyl cellulose, and with cellulose acetate in the ratio of 60 parts of the polymer to 20 parts of the acetate.

It is to be observed that although the alkylene oxides can be polymerized by a large number of agents such as calcium chloride, metallic sodium, ultra violetlight. etc., these agents are ineilec- 25 tive for polymerizing cyclohexene'oxide, and the other oxides mentioned herein.

The present invention is applicable to all carbocyclic epoxy compounds in which the oxygen is linked to adjacent carbon atoms which are 30 both members of a carbocyelie group. I may for instance use alkyl substituted cyclohexene oxides, e. g., methyl, dimethyl, isopropyl, butyl, etc., cyclohexene oxides as well as dlhydronaphthalene oxides. Partially or completely hydrogen- '35 ated substituted or v unsubstituted dihydronaphthalene oxides may also be used. Carbocyclic epoxy compounds containing less than six carbon atoms may also be used. Compounds of the kind mentioned herein may beinterpoly- 40 merized, as for instance by using any combination of these compounds. The preferred materials,

however, are the carbocyclic epoxy compoimds of thehydroaromatic seriessuch as cyclohexene oxide.

' v 45 As vmany apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that I do not limit myself to the specific embodiments thereof except as defined 5o in the appended claims.

1. A process for producing polymers which comprises heating in the presence-of a catalyst an epoxy compound in which the oxygen is linked 55 I to eiiec-ent carbon atoms in e cerbccyclic ring, and ccntin the heating until said epoxy eompcund is polymerized, said ceteiyst being selected from the class of active earths and cieys.

2. In a. process for making resins from cyclohexene oxide the step which comprises heating cyciohexene oxide with an active earth.

R0 EIIL. 

